CHARACTERISATION OF SOME AGRICULTURAL WASTE

BIOREFINERY FRACTIONATION PRODUCTS

ADRIAN CTLIN PUIEL, BOGDAN MARIAN TOFNIC
GHEORGHE ASACHI TECHNICAL UNIVERSITY OF IAI, FACULTY OF CHEMICAL ENGINEERING AND ENVIRONMENTAL PROTECTION, DEPARTMENT OF NATURAL AND SYNTHETIC
POLYMERS, 71 A MANGERON BVD, 700050 - IAI, ROMANIA
puitelac@ch.tuiasi.ro; adrianpuitel@gmail.com

INTRODUCTION
The integrated lignocellulosics biorefinery: an integrated production facility which uses biomass as raw material. Vegetal resources are lignocellulosic biorefinerys feedstock for fractionation
into materials such as: cellulose fibers, lignin, chemicals, bio-fuels and energy (Friedl, 2012). The pulp and paper industry is making use of a renewable feedstock and is considered a first
generation biorefinery (Sousa, 2010). Nonwood agricultural waste fiber sources advantages over wood are: lower lignin content, availability and shorter growing cycle (Leponiemi, 2008; Hedjazia
et al. 2009; Tofanic et. al., 2012). Agricultural waste are an economically feasible source of virgin fiber if appropriate process conditions are selected (Rousu et al., 2002; Pedersen and Meyer, 2010;
Sanchez et al. 2010; Sanchez et al., 2010; MADR, 2012).
Our work focuses on the characterization of some agricultural waste (oat straws Avena sativa and rapeseed stalks Brassica napus L.) biorefining fractionation products. Alkaline pulping was
employed for the fractionation and butanol was introduced in the liquid phase to enhance selectivity and efficiency of the process. Obtained pulp fibers were analyzed from the perspectives of obtaining
different paper products. Lignin is the second important biomass component and has an enormous potential for conversion to chemicals and energy therefore a significant part of the work is dedicated to
its study by GPC/HPSEC and FTIR. These data are useful in the process of the establishing of these lignins valuing directions.

EXPERIMENTAL SET-UP, RESULTS AND DISCUSSIONS

Rapeseed stalks (Brassica napus)
Oat straws (Avena sativa)

Chemical component

Cellulose Lignin

Hemicelluloses

Organic
solvent
extractives

Ash

Plant species

Rapeseed stalks
(Brassica napus L)
Oat straws
(Avena sativa)

Chemical composition analysis

Pulping experiments parameters

47.2

580

31.2

2.11

2.47

115

36.4

830

45.3

1.73

1.82

101

Na2CO3C4H9OH

42

53

520

15.8

1.59

2.48

96

RAPESEED
STALKS

OAT STRAW

OAT STRAW

Tensile
CCT-30
SCT
CMT-30
index
(KN/m)
(KN/m)
(N)
(kNm/kg) SCAN P42 ISO 9895 ISO 7263
ISO 1924-2

29.8

23

640

62

1.83

2.78

99

SodaC4H9OH

32

15

750

72

2.18

3.15

138

Na2CO3C4H9OH

34

42

630

58.5

2.41

2.93

153

1114.85

1085.92

1045.42

Pulping process

Mn

Mw

Polydispersity
index

596

1041.56

2000

1900

1800

1700

1600

1500

1100

1000

900

800

700

600

773.45

603.72

653.87
896.9
1037.7

500

2200

2100

2000

1900

1800

1700

1600

1500

1400
1300
Wavenumber (cm-1)

1100

1000

900

800

534.28

711.73

754.17

800.46

831.32

611.43
1200

574.79

1116.78

1082.06

1220.94

1261.44
1330.88

1377.17

1460.11
1421.53

1400
1300
1200
Wavenumber (cm-1)

Rape seed
stalks (Brassica
napus)

538.14

1083.99

1120.64
1157.29

1244.08
1219.01

1269.16

1330.88

1379.1

1462.04

1423.46

1639.49

1514.12

1708.93
1641.42

1512.19

1699.28

621.08

871.82

2100

580.57

1219.01
1336.67

1363.67

1151.5

1645.28

1514.12

1460.11

1707

599.86
572.86
542
702.09
810.1

532.35

621.08
731.02
705.95

850.61
817.82

920.04
896.9

1118.71

1041.56

1219.01
1155.36

1269.16

1425.39

1219.01

1118.71

1267.23

991.41

1363.67

1328.95

1155.36

1269.16

1089.78

1219.01

1043.49

1120.64

25

898.83

Organic phase
THF on
TSK GEL
GMHHR-M
30X7.8
Exclusion limit
4106 Da
(polystyrene
standards-Fluka)

RAPESEED
STALKS

3.9

43

1554.62

20

Elution volume, mL

2200

Lignin source

2.2

44

Typical chromatograms data obtained for the elution of the black

liqueur separated lignins were used for the calculations of the relative
molecular weights and polydispersity.
Aqueous phase
(pH12 buffer
solution)
TSK GEL
GMPWXL
30X7.8
500-8106 Da
(calibration with
poly(sodium 4styrenesulfonate
) standards
Fluka)

26.8

SodaC4H9OH

551.64

15

18.4

Soda

1041.56

1151.5

1325.09

1363.67

1089.78

1639.49
1620.2

1712.78

1516.05

1460.11
1425.39

1514.12

1462.04

1600.91

10

1639.49
1604.77

0.0
5

39.1

Intrinsic
viscosity
(cm3/g)
ISO 5351

OS.esp

732.95

25

Elution volume, mL

5.8

Kappa
number
ISO 302

OSB.esp

846.75
827.46

20

1423.46

1649.13
RS.ESP

1716.64

15

4.5

Pulp
yield
(%)

Soda

OCB.esp

0.4

0.2

10

Oat straw

1712.78

0.6

0.0
5

Pulping
process
reagents

Rapeseed
stalks

RSB.esp

1363.67
1328.95

0.2

0.8

1514.12

0.4

rapeseed stalks soda acetylated lignin

oat straw soda acetylated lignin
rapeseed stalks soda-butanol acetylated lignin
oat straw soda-butanol acetylated lignin
rapeseed stalks carbonate-butanol acetylated lignin
oat straw carbonate butanol acetylated lignin

1.0

1462.04

0.6

1.2

1425.39

Normalised detector signal at 280 nm

Normalised detector signal at 280 nm

Rapeseed stalk soda lignin

Oat straw soda lignin
Rapeseed NaOH-butanol lignin
Oat straw NaOH-butanol lignin
Rapeseed carbonate butanol lignin
Oat straw carbonate butanol lignin

31

Note: mechanical properties have been determined after beating (1500 rpm). The achieved beating degree values
ranged from 55 to 60oSR; CCT Corugated crush test; SCT Short span compression test; CMT- Concora medium test
RCB.esp

0.3mL/min, detection UV-280nm

Actylation of samples eluted with organic solvents (THF)
0.8

Sample

FT-IR analysis
KBr pellet
Digilab-Scimitar FTS2000

Molecular weight distribution study

on GPC/HPSEC TSKGEL columns

1.0

21.5

Pulp characteristics and laboratory sheets mechanical properties

Temperature 170oC;
Heating time 45 minutes; Cooking time 60 minutes;
Solid to liquid ratio: 1:5;
Alkali charges as NaOH
Soda (20% NaOH)
Soda-butanol (20% NaOH; C4H9OH,10% liquid phase);
Sodium carbonate/butanol (24%Na2CO3 C4H9OH,10% liquid phase).

Lignin separation
from black
liquor
(pH 2 acid precipitation)

41

700

600

Assignment

Oat straws
(Avena
sativa)

Soda (RS)

22762

62634

2.75

Soda-C4H9OH (RSB)

18650

57221

3.06

cm-1

Na2CO3- C4H9OH (RCB)

8491

28351

3.34

3417

Hydroxyl in phenols and alcohols

3427

cm-1

Soda (OS)

21769

54073

2.48

2935, 2843

CH link symmetric and asymmetric secondary C atoms

2935

Soda-C4H9OH (OSB)

17976

48651

2.72

1716

Unconjugated C=O stretching

1712

Na2CO3- C4H9OH (OCB)

9490

36780

3.87

1640

Conjugated C=O stretching

1640

Aromatic ring vibrations

1604; 1514
1460

Soda (RS)

1770

6403

3.61

1604; 1514

Soda-C4H9OH (RSB)

9446

109817

11.6

1462

CH in aromatic CH3

Na2CO3- C4H9OH (RCB)

2572

11402

4.43

1420

Aromatic ring vibrations and possible OH in diols

1421

Soda (OS)

1889

6557

3.47

1328

Syringil ring breathing with C=O stretching

1320; 1336

Soda-C4H9OH (OSB)

1900

6607

3.48

Na2CO3- C4H9OH (OCB)

1839

6235

3.39

It can be observed that significant differences between the two types of

columns were obtained. The molecular weight values of the non-acetylated
lignins sample appear to be higher than those of the acetylated lignin samples.
The reasons for these include the possible interactions between lignin
macromolecules (associations) causing apparent higher molecular weight
values. Acetylation changes the order of the decrease of molecular weights
with the highest values obtained for the soda butanol pulping samples which
also had increased polydispersity.

1269;1219

Guaiacyl ring breathing with C=O stretching

C-O in ester and ether linkages

1269; 1244

1155, 1118

CH in plane deformations both guayacil and syringil types

1150;1114

~1041

C-O in ethers and diols

~1037

830

CH out of plane

~837

500

As compared to other low carbon number alcohols, butanol

has a higher than water boiling point and is not miscible with it
at room temperature. Use of butanol in soda pulping has
leaded to an increase in both yield and viscosity for both
categories of raw materials used. At same alkali charge, the
kappa number obtained by soda-butanol pulping was lower.
Butanol facilitates the impregnation process and may enhance
lignin reactivity. The possibility of replacing of sodium
hydroxide as alkali source was tested by replacing it with
sodium carbonate. Since carbonate is less alkaline than
sodium hydroxide, the initial test performed at 20% (as NaOH
equivalents) alkali charge did not lead to fiber separations.
The obtained pulps were processed by beating and
laboratory test sheets were obtained. Tensile index increased
by adding butanol in the experiments where soda was used as
alkali source. In case of sodium carbonate-butanol pulps, the
tensile index values remained lower due to the higher lignin
content which is known to be rigid and hydrophobic and
preventing the formation of hydrogen fiber linkages.
The values on the raw materials and of obtained pulps
characteristics uphold not only their usability, but also the
economic practicability and environmental security of many
processes involving their use in a biorefinery concept
approach. The primary use of the obtained cellulose pulp could
be as raw virgin fiber in papermaking, which in some cases is
already facing some problems induced by recovered paper
prolonged usage. The results on mechanical properties testing
indicate their potential use as raw materials for different sorts
of packaging paper such as fluting paper or liners and
cardboards for further processing to corrugated cardboard
boxes or other types of paper packaging.

The FT-IR spectra did show some changes due to the use of butanol such as increased absorbance of the band at 1510 cm-1,
indicating a possible increase in aromatic character of lignin and also increased absorbances of the bands at ~1150 cm-1 and
~1040 cm-1 indicate possible formation of ethers by butanol reaction with the free hydroxyl groups during soda-butanol pulping.
Both of the spectra series display the characteristic bands of alkali lignin.

REFERENCES
MADR (2012) - Romanian Ministry of Agriculture and Rural Development Agriculture in economy, available on line: http://www.madr.ro/images/agricultura/agricultura-romaniei-aprilie-2012.pdf.
Friedl, A. (2012) Lignocellulosic Biorefinery, Environmental Engineering and Management Journal, 11, (1), 75-79
Hedjazia, S., Kordsachiab, O., Patt, R., Latibarid, A.J., Tschirnere, U. (2009) Alkaline sulfiteanthraquinone (AS/AQ) pulping of wheat straw and totally chlorine free (TCF) bleaching of pulps. Industrial Crops and Products, 29(1), 27-36.
Leponiemi, A. (2008). Non-wood pulping possibilities - a challenge for the chemical pulping industry, Appita Journal, 61 (3), 235-243.
Tofanica, B.M., Cappelletto, E., Gavrilescu, D. , Mueller K. (2011). Properties of Rapeseed (Brassica napus) Stalks Fibers. Journal of Natural Fibers, 8(4), 241-262.
Pedersen, M., Meyer, A.S. (2010) Lignocellulose pretreatment severity relating pH to biomatrix opening, New Biotechnology, 27,(6), 739-750.
Rousu, P., Pivi, P., Anttila, J. (2002) Sustainable pulp production from agricultural waste, Resources, Conservation and Recycling, 35, (12), 85-103.
Snchez, R., Rodrguez A., Navarro E., Conesa J.A., Jimnez L. (2010). Use of Hesperaloe funifera for the production of paper and extraction of lignin for synthesis and fuel gases, Biomass Bioenergy, 34, 1471-1480.
Sousa, G.D.A. (2010) Biorefinery development pathways: a survey for the pulp and paper industry, Proceedings of XXI Encontro Nacional da TECNICELPA / VI CIADICYP 2010-12, 15 Outubro 2010 - Lisboa, Portugal